CN105914388A - Lead methanesulfonate flow battery electrolyte - Google Patents
Lead methanesulfonate flow battery electrolyte Download PDFInfo
- Publication number
- CN105914388A CN105914388A CN201610246329.5A CN201610246329A CN105914388A CN 105914388 A CN105914388 A CN 105914388A CN 201610246329 A CN201610246329 A CN 201610246329A CN 105914388 A CN105914388 A CN 105914388A
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- Prior art keywords
- electrolyte
- battery
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- acid lead
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0002—Aqueous electrolytes
- H01M2300/0005—Acid electrolytes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
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Abstract
The invention discloses an application of NaF as an additive in a lead methanesulfonate flow battery electrolyte. The electrolyte is a mixture liquid of lead methanesulfonate and methanesulfonic acid, wherein the concentration of the (CH3SO3)2Pb is 0.1-2 M, the concentration of the CH3SO3H is 0-1 M and the concentration of the NaF is 0.005-0.02 M. The NaF, as the additive, prolongs the service life and improves Coulomb efficiency of a battery, wherein the service life of the battery can reach more than 1000 times, the Coulomb efficiency is basically more than 90%, and energy efficiency is higher than 78%.
Description
Technical field
The present invention relates to flow battery field, a kind of can improve making of pyrovinic acid lead flow battery
With life-span and the electrolysis additive of coulombic efficiency, and this additive is in pyrovinic acid lead flow battery
Application.
Background technology
The fast development of global economy so that the demand for the energy constantly increases and primary energy is supplied not
Foot, so developing other regenerative resources (wind energy, solar energy etc.) to become focus of concern.But
These regenerative resources face fluctuation, intermittence and the uncertain factor such as dispersiveness, randomness and restrict its
Development, so that high-efficiency energy-storage technology solves renewable energy power generation Unsteady characteristics.With other energy storage skill
Art is compared, and flow battery is more suitable for regenerative resource electric energy electric power storage and conversion.It has many excellent features:
Capacitance of storage is big, energy efficiency is high, activation polarization is little, can deep discharge, can realize fast charging and discharging,
The advantages such as the feature of environmental protection is good, it is adaptable to extensive electric power storage.This pyrovinic acid lead flow battery used by invention belongs to
In one full appositional pattern single flow battery.
Pyrovinic acid lead flow battery is with acidic methylene sulfonic acid lead as electrolyte, and both positive and negative polarity all uses conduction poly-
Compound based composites.Electrolyte and battery are independently placed, and electrolyte is transferred to inside battery by pump.?
Pb solvable during charging2+Aoxidize on positive and negative electrode respectively, reduction reaction generates PbO2With Pb sinking
Amassing at electrode surface, during electric discharge, positive and negative deposit aoxidizes, reduction reaction generates Pb2+It is dissolved in electrolysis
In liquid.When discharge and recharge, on positive and negative electrode, there are electric field, velocity field, temperature and concentration etc. common in battery
Effect.
The concrete reaction principle of pyrovinic acid lead flow battery is as follows:
Positive pole: Pb2++2H2O-2e→PbO2+4H+, E0=1.455V;
Negative pole: Pb2++ 2e → Pb, E0=-0.126V;
Overall reaction: 2Pb2++2H2O→Pb+PbO2+4H+;
Pyrovinic acid lead flow battery does not uses the expensive material such as amberplex because having, and structure simplifies, ratio
The particular advantages such as energy is high and there is the biggest development prospect.But pyrovinic acid lead flow battery there is also one
A little not enough: service life cycle is short, positive pole electrodeposit brown lead oxide is easy to fall off, energy efficiency and reserve of electricity
It is also required to improve further etc. performance.By substantial amounts of experiment and literature research, at pyrovinic acid lead liquid flow electricity
The method adding additive NaF in the electrolyte in pond can not only improve battery performance, and economical, effectively.
Additive NaF can extend the discharge and recharge life-span of battery and improve the coulombic efficiency of battery.
Sodium fluoride is white powder, is dissolved in water, and the aqueous solution is alkalescent, low price, is a kind of good
Electrolysis additive.Additive NaF is incorporated into electrolyte and the impact of battery performance is mainly being improved battery just
Pole deposit PbO2Electro catalytic activity and stability.Battery is F when charging-Ion can enter into positive pole and sink
Long-pending thing PbO2Intracell.Replace a part of oxygen atom, form F-PbO2Complex, occupies free oxygen atom
The passage of diffusion, therefore inhibits at electrode interface nascent state free oxygen atom to PbO2Bulk diffusion.One side
Face, maintains PbO2The stoichiometric number of middle oxygen is less than 2, maintains oxygen vacancies concentration, is conducive to maintaining electricity
The stability of pole.On the other hand, effectively avoid deterioration and basic unit's oxidation of coating character, and suppress
PbO2Anodic solution, extend PbO2Anode life.Therefore electrolysis additive NaF can improve
The coulombic efficiency of pyrovinic acid lead flow battery and service life.
Summary of the invention
It is an object of the invention to overcome pyrovinic acid lead flow battery to presently, there are short the lacking of service life cycle
Point, improves the performance of battery in terms of electrolysis additive, adds and add in pyrovinic acid lead electrolytic solution
Add anode reactant PbO when agent NaF can improve battery charging2Electro catalytic activity and stability, thus carry
Coulombic efficiency that high battery is overall and discharge and recharge life-span.NaF additive improves life-span and the coulomb of battery
Efficiency, wherein the life-span of battery can reach more than 1000 times, coulombic efficiency substantially more than 90%, energy
Efficiency is more than 78%.
Pyrovinic acid lead fluid cell electrolyte, for assembling in the battery of use, described assembles the battery used
Including with lower part:
Base plate: base plate uses aluminum alloy plate materials, is used for fastening pile, prevents electrolyte from revealing, size
For: 12.5cm × 10.5cm.
Positive and negative pole plate: positive/negative plate uses PVC material, size is: 12cm × 10cm, positive and negative
Milling out size in the middle of pole plate is: 2cm × 5.8cm, and thickness is the groove of 4mm, is used for embedding conducting polymer base multiple
Condensation material electrode.
Runner: the exterior contour of runner is identical with the area of positive and negative pole plate, the area of inner flow passage and conduction
The effective area of plate is identical.
Positive and negative electrode conductive plate: the conducting polymer based composites that positive and negative electrode conductive plate all uses, will lead
Electric polymer base composite board and copper mesh be tailored into 2cm × 5.8cm size together with wire at 200-250 DEG C and
5-10kgf/cm2Hot-forming and cool to the furnace take out after normal temperature.Conductive plate after hot pressing is repaired further
Become original size 2cm × 5.8cm.
Battery assembles: by positive and negative conductive plate silica gel sealing to the groove of positive and negative pole plate, to prevent electricity
Solve the leakage of liquid.Order screw rod group according to aluminum alloy bottom plate-positive plate-runner-negative plate-aluminum alloy bottom plate
Dress.
According to an aspect of the present invention, the invention provides a kind of pyrovinic acid lead fluid cell electrolyte,
Described pyrovinic acid lead fluid cell electrolyte is by (CH3SO3)2Pb、CH3SO3H, purified water and additive NaF
Composition, wherein (CH3SO3)2The concentration of Pb is 0.1-2M, CH3SO3The concentration of H is the dense of 0-1M, NaF
Degree is 0.005-0.02M.
Preferably, (CH3SO3)2The concentration of Pb is 1.5-1.8M, CH3SO3The concentration of H is 0.3-0.9M,
The concentration of NaF is 0.01-0.015M.
According to another aspect of the present invention, the invention provides a kind of pyrovinic acid lead fluid cell electrolyte
Preparation method, first deionized water is slowly added into CH3SO3H dilutes, then at PbCO3Add
A small amount of deionized water, by the CH after dilution3SO3H is slowly added to PbCO3In the aqueous solution and ceaselessly
Stirring, until reaction is completely, adds deionized water and dilutes to obtain the most additivated electrolyte;
In the most additivated electrolyte, add NaF additive again, after stirring, obtain pyrovinic acid lead
Fluid cell electrolyte.
Charge-discharge procedures is arranged: charging and discharging currents density is 10-40mA/cm2, charging interval 0.5-2h, electrolysis
Liquid line flow velocity in the battery is 0.5-5cm/s.
Compared with prior art, due to the fact that employing NaF as electrolysis additive, containing this interpolation
The pyrovinic acid lead flow battery of agent improves anode deposit PbO2Electro catalytic activity and stability, and
And extend the anode life of brown lead oxide.Thus additive NaF improve battery coulombic efficiency and make
Use the life-span.Special is 10mA/cm in the density of charging current2, the battery when amount of additive NaF is 0.01M
The coulombic efficiency of discharge and recharge substantially more than 90%, energy efficiency is more than 78%, and battery life reaches 1000
Secondary.
Accompanying drawing explanation
Fig. 1 is the coulombic efficiency of A battery and the figure of cycle-index in example 1;
Fig. 2 is the energy efficiency of A battery and the figure of cycle-index in example 1;
Fig. 3 is the coulombic efficiency of B battery and the figure of cycle-index in example 1;
Fig. 4 is the energy efficiency of B battery and the figure of cycle-index in example 1;
Fig. 5 is the coulombic efficiency of C battery and the figure of cycle-index in example 2;
Fig. 6 is the energy efficiency of C battery and the figure of cycle-index in example 2;
Fig. 7 is the coulombic efficiency of D battery and the figure of cycle-index in example 2;
Fig. 8 is the energy efficiency of D battery and the figure of cycle-index in example 2.
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention of greater clarity, below in conjunction with specific embodiment party
Formula, the present invention is described in more detail.It should be understood that these describe the most exemplary, and do not really want
Limit the scope of the present invention.
Embodiment 1
The electrolyte of preparation pyrovinic acid lead flow battery in fume hood:
1) deionized water is slowly added into CH3SO3H dilutes, then at PbCO3Add go on a small quantity from
Sub-water, by the CH after dilution3SO3H is slowly added to PbCO3In the aqueous solution and be continuously agitated, directly
To reaction completely, add deionized water and dilute to obtain the most additivated electrolyte;Wherein (CH3SO3)2Pb is
1.8mol:CH3SO3H is 0.3mol, altogether 1L.
2) the most averagely pour in the electrolyte bottle of two 500ml.
A electrolyte: add the NaF of 0.005mol in the 500ml electrolyte just now prepared, uniform stirring,
Electrolyte as pyrovinic acid lead flow battery.
B electrolyte: without any additive.
Pyrovinic acid lead flow battery assembles in the manner described above, carries out even with A, B electrolyte and pump pipe
Connect, fully put test.The parameter of charge-discharge test is arranged: charging and discharging currents density is 10mA/cm2,
Charging interval 2h, electrolyte line flow velocity in the battery is 0.5-5cm/s.Result display A electrolyte adds
The battery coulombic efficiency of 0.005mol NaF is more than 90%, and energy efficiency is 78-85%, the charge and discharge cycles longevity
Life is 1000 times.The coulombic efficiency of B battery is 70-90%, and energy efficiency is 60-80%.
Embodiment 2
The electrolyte of pyrovinic acid lead flow battery is prepared: method is with embodiment 1, wherein in fume hood
(CH3SO3)2Pb:CH3SO3H=1.5:0.9 (M), altogether 1L.
Pour into respectively in the electrolyte bottle of two 500ml.
C electrolyte: add the NaF of 0.0075mol, uniform stirring in the electrolyte just now prepared, use
Make the electrolyte of pyrovinic acid lead flow battery.
D electrolyte: without any additive.
Pyrovinic acid lead flow battery assembles in the manner described above, carries out even with C, D electrolyte and pump pipe
Connect, fully put test.The parameter of charge-discharge test is arranged: charging and discharging currents density is 10mA/cm2,
Charging interval 2h, electrolyte line flow velocity in the battery is 0.5-5cm/s.The coulomb effect of result display C battery
Rate is 90-91%, and energy efficiency is 74-77%.The coulombic efficiency of D battery is 70-90%, and energy efficiency is
50-80%.
Claims (4)
1. a pyrovinic acid lead fluid cell electrolyte, described pyrovinic acid lead flow battery is electrolysed
Liquid is by (CH3SO3)2Pb、CH3SO3H, purified water and additive NaF composition, wherein (CH3SO3)2Pb
Concentration be 0.1-2M, CH3SO3The concentration of H be the concentration of 0-1M, NaF be 0.005-0.02M.
Pyrovinic acid lead fluid cell electrolyte the most according to claim 1, it is characterised in that:
(CH3SO3)2The concentration of Pb is 1.5-1.8M, CH3SO3The concentration of H is the dense of 0.3-0.9M, NaF
Degree is 0.01-0.015M.
Pyrovinic acid lead fluid cell electrolyte the most according to claim 1, it is characterised in that:
Its preparation method comprises the following steps:
1) battery electrolyte according to claim 1 composition, first by deionized water lentamente
Join CH3SO3H dilutes, then at PbCO3Add a small amount of deionized water, after dilution
CH3SO3H is slowly added to PbCO3In the aqueous solution and be continuously agitated, until reaction is completely,
Add deionized water and dilute to obtain the most additivated electrolyte;
2) in the most additivated electrolyte, add NaF additive, after stirring, obtain methyl
Sulfonic acid lead fluid cell electrolyte.
Pyrovinic acid lead fluid cell electrolyte the most according to claim 1, it is characterised in that:
Pyrovinic acid lead fluid cell electrolyte, for assembling in the battery of use, described assembles the battery used
Including with lower part:
Base plate: base plate uses aluminum alloy plate materials, is used for fastening pile, prevents electrolyte from revealing,
A size of: 12.5cm × 10.5cm;
Positive and negative pole plate: positive/negative plate uses PVC material, a size of: 12cm × 10cm,
Milling out a size of in the middle of positive/negative plate: 2cm × 5.8cm, thickness is the groove of 4mm, is used for embedding conduction
Polymer matrix composite electrode;
Runner: the exterior contour of runner is identical with the area of positive and negative pole plate, the area of inner flow passage with
The effective area of conductive plate is identical;
Positive and negative electrode conductive plate: the conducting polymer based composites that positive and negative electrode conductive plate all uses,
Conducting polymer base composite board and copper mesh are tailored into 2cm × 5.8cm size together with wire
200-250 DEG C and 5-10kgf/cm2Hot-forming and cool to the furnace take out, after hot pressing after normal temperature
Conductive plate is trimmed to original size 2cm × 5.8cm further;
Battery assembles: by positive and negative conductive plate silica gel sealing to the groove of positive and negative pole plate, in case
The only leakage of electrolyte, according to the order of aluminum alloy bottom plate-positive plate-runner-negative plate-aluminum alloy bottom plate
Assemble with screw rod.
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CN201610246329.5A CN105914388A (en) | 2016-04-20 | 2016-04-20 | Lead methanesulfonate flow battery electrolyte |
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CN201610246329.5A CN105914388A (en) | 2016-04-20 | 2016-04-20 | Lead methanesulfonate flow battery electrolyte |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106711486A (en) * | 2016-12-13 | 2017-05-24 | 华中科技大学 | Lead redox flow battery electrolyte |
CN108832164A (en) * | 2018-05-28 | 2018-11-16 | 华中科技大学 | A kind of lead fluid cell electrolyte containing compound additive |
CN109873191A (en) * | 2019-03-29 | 2019-06-11 | 西安理工大学 | A kind of electrolyte and preparation method thereof of the resistance to season of lead flow battery |
CN110190312A (en) * | 2019-06-25 | 2019-08-30 | 西安理工大学 | A kind of lead flow battery electrolyte |
CN112838255A (en) * | 2021-01-28 | 2021-05-25 | 西安理工大学 | Efficient stable electrolyte of lead single flow battery and preparation method thereof |
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CN102723519A (en) * | 2011-03-30 | 2012-10-10 | 中国人民解放军63971部队 | Lead liquid flow battery electrolyte |
CN102723518A (en) * | 2011-03-30 | 2012-10-10 | 中国人民解放军63971部队 | All-lead liquid flow battery |
US20150180088A1 (en) * | 2012-07-20 | 2015-06-25 | Commissariat A L'energie Atomique Et Aux Energies Alternatives | Electrochemical lead battery including a specific additive |
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US4400449A (en) * | 1980-01-10 | 1983-08-23 | Peter O. Henk | Lead salt electric storage battery |
CN101567459A (en) * | 2008-04-25 | 2009-10-28 | 北京化工大学 | Acid single flow cell |
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Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106711486A (en) * | 2016-12-13 | 2017-05-24 | 华中科技大学 | Lead redox flow battery electrolyte |
CN106711486B (en) * | 2016-12-13 | 2020-05-19 | 华中科技大学 | Lead flow battery electrolyte |
CN108832164A (en) * | 2018-05-28 | 2018-11-16 | 华中科技大学 | A kind of lead fluid cell electrolyte containing compound additive |
CN109873191A (en) * | 2019-03-29 | 2019-06-11 | 西安理工大学 | A kind of electrolyte and preparation method thereof of the resistance to season of lead flow battery |
CN109873191B (en) * | 2019-03-29 | 2021-06-15 | 西安理工大学 | Lead flow battery seasonal-resistant electrolyte and preparation method thereof |
CN110190312A (en) * | 2019-06-25 | 2019-08-30 | 西安理工大学 | A kind of lead flow battery electrolyte |
CN110190312B (en) * | 2019-06-25 | 2021-01-15 | 西安理工大学 | Electrolyte for lead flow battery |
CN112838255A (en) * | 2021-01-28 | 2021-05-25 | 西安理工大学 | Efficient stable electrolyte of lead single flow battery and preparation method thereof |
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